Patent GB-1007755-A (GB)
Title: New organo-phosphorus esters and pesticidal compositions containing them
Inventor: SIRRENBERG WILHELM
IPC: C07F9/12
Filed: 1962-06-06
Abstract: The invention comprises esters of the general formula <FORM:1007755/C2/1> wherein R1 and R2 which may be the same or different are selected from unsubstituted or substituted saturated or unsaturated aliphatic, cyclo-aliphatic, araliphatic or aromatic radicals, which can be linked to the phosphorus atom directly or through an oxygen atom, and N,N-disubstituted amino groups, Ar is an unsubstituted or substituted arylene radical, R is an unsubstituted or nuclear substituted aryl or aralkyl radical or an <FORM:1007755/C2/2> group in which Ar1 is an unsubstituted or substituted arylene radical and R1 and R2 are as defined above, X is an O or S atom and n is O when X is a sulphur atom or n is O or 2 when X is an oxygen atom with the proviso that when R1 is an aliphatic or atomatic radical directly linked to the phosphorus atom and R2 is an aliphatic radical linked to the phosphorus atom via an oxygen atom or when R1 and R2 are both aliphatic radicals linked to the phosphorus atom via oxygen and n is O then R is an aralkyl radical or a group of the general formula <FORM:1007755/C2/3> in which Ar, R1, R2 and X are as defined above. They may be obtained by reacting an appropriate unsubstituted or substituted mono- or dihydroxy diaryl- or monohydroxy aryl-aralkyl sulphide or sulphone with an acid halide of the general formula: R1R2P(X).Hal and if desired oxidizing the sulphide to the corresponding sulphone.  The reaction is preferably carried out at elevated temperature in an inert organic solvent, e.g. acetone, methyl ethyl ketone, methyl isopropyl ketone or acetonitrile, and in the presence of an acid-binding agent. Alternatively, the reaction may be carried out in the absence of an acid-binding agent by using the alkali metal or ammonium salts of the sulphide or sulphone.  A small amount of copper powder may be included in the reaction mixture to accelerate the reaction. The sulphide product may be converted to the sulphone by oxidation with H2O2, potassium permanganate, nitric acid or a hypohalogenous acid.  The arylene radical Ar and the aryl or alkyl radical R can be substituted in the nucleus, e.g. by halogen atoms, and/or alkyl, alkoxy, alkylmercapto, hydroxy, carbalkoxy, nitro or cyano groups.  Several examples are given and the products have pesticidal properties (see Division A5). Specifications 812,530 and 819,689 are referred to.ALSO:A pesticidal composition or plant protection agent comprises a solid or liquid carrier or diluent and a phosphorous-containing ester of the general formula:- <FORM:1007755/A5-A6/1> wherein R1 and R2 which may be the same or different are selected from unsubstituted and substituted, saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic radicals, which can be linked to the phosphorus atom directly or through oxygen, and N, N-disubstituted amine groups, Ar is an unsubstituted or substituted arylene radical, R is an unsubstituted or nuclear substituted aryl or aralkyl radical or an <FORM:1007755/A5-A6/2> group in which Ar1 is an unsubstituted or substituted arylene radical and R1 and R2 are as defined above, X is an oxygen or sulphur atom and n is 0 when X is sulphur or n is 0 or 2 when X is oxygen, with the proviso that when R1 is an aliphatic or aromatic radical directly linked to the P atoms and R2 is an aliphatic radical linked to the P atom via an oxygen atom or when R1 and R2 are both aliphatic radicals linked to the P atom via oxygen atoms and n is 0 then R is an aralkyl radical or a group of the formula <FORM:1007755/A5-A6/3> as defined about (see Division C2). The arylene radical Ar and the aryl or aralkyl radical R can be substituted in the nucleus by e.g. halogen atoms and/or alkyl, alkoxy, alkylmercapto, hydroxy, carbalkoxy, nitro and cyano groups. Specified carriers or diluents are talc, chalk, bentonite, clay, water, alcohols, ketones and liquid hydrocarbons.  Known insecticides and/or fertilizers may also be present.  A suitable composition is obtained by mixing the active ingredient with acetone, adding an emulsifier and then diluting with water.  Specifications 812,530 and 819,689 are referred to.